EP0018161B1 - Aldéhyde-éthers et procédé pour leur préparation - Google Patents

Aldéhyde-éthers et procédé pour leur préparation Download PDF

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Publication number
EP0018161B1
EP0018161B1 EP80301129A EP80301129A EP0018161B1 EP 0018161 B1 EP0018161 B1 EP 0018161B1 EP 80301129 A EP80301129 A EP 80301129A EP 80301129 A EP80301129 A EP 80301129A EP 0018161 B1 EP0018161 B1 EP 0018161B1
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Prior art keywords
rhodium
catalyst
absolute
hydrogen
hydroformylation
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EP80301129A
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German (de)
English (en)
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EP0018161A1 (fr
Inventor
Norman Harris
Alan James Dennis
George Edwin Harrison
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Johnson Matthey Davy Technologies Ltd
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Davy Mckee London Ltd
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Priority to AT80301129T priority Critical patent/ATE3537T1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/198—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/188—Unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide

Definitions

  • This invention relates to novel aliphatic aldehyde-ethers and to their preparation.
  • British Patent Specification No. 1448090A teaches a catalytic hydroformylation process employing a rhodium coordination complex. 54 Examples are included. At the end of the specification there is given a speculative list of other substrates which are said to yield aldehydes in the process described. This list mentions allyl ethyl ether but gives no details of the yield to be expected. However, in the light of the Adkins and Krsek article, low yields can be expected. The list of possible substrates also mentions in precedence to allyl ethyl ether, allyl alcohol and butadiene as possible substrates.
  • Allyl alcohol in practice is either itself a deactivator of the rhodium complex hydroformylation catalyst or else produces a catalyst deactivator amongst the byproducts. At all events it is impractical to use allyl alcohol as feedstock in a continuously operated commercial hydroformylation process using a rhodium complex catalyst because essentially complete catalyst deactivation occurs after a short period of operation. Butadiene is also a catalyst inhibitor for the rhodium complex hydroformylation catalysts of British Patent Specification No. 1448090A.
  • British Patent Specification No. 1298331 A teaches a hydroformylation process that employs a rhodium complex catalyst.
  • the specification lists 7 Examples. It also includes a list of olefinically unsaturated compounds which can be hydroformylated in the process described. No details of yields or specific reaction conditions are given. Included in this list are allyl alcohol, a compound which cannot be used as feedstock in a continuously operated rhodium catalysed hydroformylation process, besides allyl ethers.
  • German Patentschrift 891690 teaches a process for making beta-alkoxyaldehydes, such as beta- methoxypropionaldehyde and beta-ethoxybutyraldehyde, by reaction of acrolein or crotonaldehyde with normal alcohols, such as methanol and ethanol. Besides methanol and ethanol other normal alcohols that are mentioned include n-propanol and n-butanol.
  • the present invention is based upon the surprising discovery that allyl t-allyl and -cycloallyl ethers can be hydroformylated in high yield using a rhodium complex hydroformylation catalyst without formation of significant quantities of byproducts that are catalyst deactivators to give a mixture of n-and iso-aldehyde ethers which are useful intermediates in the production of other commercially important chemicals, such as butane-1,4-dioi, tetrahydrofuran, and gamma-butyrolactone.
  • Particularly preferred compounds of formula (I) are: and
  • the invention further provides a process for the preparation of a compound of formula (I) which comprises contacting a compound of the general formula: wherein R,, R 2 , R 3 and R 4 are as defined above, with hydrogen and carbon monoxide under hydroformylation conditions and in the presence of a catalytic amount of a hydroformylation catalyst.
  • the invention also extends to the compounds of formulae (V) and (VI) per se.
  • the hydroformylation catalyst may be any Group VIII metal-containing hydroformylation catalyst known to be effective for catalysing the hydroformylation of terminal olefins.
  • Typical of such catalysts are those containing, for example, cobalt, iridium, ruthenium, platinum and rhenium.
  • the catalyst is a rhodium-containing catalyst.
  • suitable reaction conditions may include use of an inert solvent, such as benzene, an operating temperature of, for example 120-125°C. a partial pressure of hydrogen of about 100 to about 150 kg/cm 2 absolute, and a partial pressure of carbon monoxide of about 100 to about 150 kg/cm 2 absolute.
  • an inert solvent such as benzene
  • a partial pressure of hydrogen of about 100 to about 150 kg/cm 2 absolute
  • a partial pressure of carbon monoxide of about 100 to about 150 kg/cm 2 absolute.
  • rhodium-containing catalyst When a rhodium-containing catalyst is used the reaction can be carried out at lower pressures, for example about 30 kg/cm 2 absolute or less, typically at about 20 kg/cm 2 absolute or less. Moreover since rhodium-containing hydroformylation catalysts are generally involatile, it is usually much easier to recover the reaction products than when using cobalt catalysts, which tend to be volatile.
  • the aldehyde-ethers of formula (I) are generally relatively volatile and can be recovered overhead from the reaction mixture.
  • the hydroformylation catalyst is a rhodium complex catalyst comprising rhodium in complex combination with carbon monoxide and a triorganophosphine ligand, such as triphenylphosphine.
  • This catalyst is preferably free from halogen, such as chlorine. Usually the catalyst will be present in solution.
  • the concentration of rhodium in the reaction medium can range from about 5 parts per million by weight up to about 1000 parts per million of rhodium or more, calculated as rhodium metal.
  • concentration lies in the range of from about 20 parts per million up to about 500 parts per million, e.g. in the range of from about 40 to about 300 parts per million, calculated as rhodium metal.
  • the rhodium may be introduced into the reaction medium in any convenient form.
  • the rhodium salt of an organic acid can be combined with the ligand in the liquid phase and then hydrogenated, prior to introduction of the compounds of formula (IV) and the hydrogen/carbon monoxide mixture.
  • the catalyst can be prepared from a carbon monoxide complex of rhodium, such as dirhodium octacarbonyl, by heating with the ligand which thereby replaces one or more of the carbon monoxide molecules. It is also possible to start with the ligand of choice and rhodium metal, or with an oxide of rhodium (e.g.
  • Rh 2 0 3 Rh 2 0 3
  • the ligand to prepare the active species in situ during the course of the hydroformylation reaction.
  • a rhodium complex such as (pentane-2,4-dionato) dicarbonyl rhodium (I) (i.e. the dicarbonyl complex of rhodium formed with acetylacetone), which is then converted under the hydroformylation conditions to the catalytic species which has been postulated to be rhodium hydridocarbonyl tris(triphenylphosphine), i.e. HRh(CO)(PPh 3 ) 3 .
  • rhodium can be introduced as HRh(CO)(PPh 3 ) 3 .
  • suitable catalyst precursors include rhodium carbonyl triphenylphosphine acetylacetonate, Rh 4 (CO), 2 and Rh e (CO) 16" Further details regarding suitable rhodium-containing hydroformylation catalysts can be obtained, for example, from United States Patent Specification No. 3,527,809.
  • the reaction can be carried out in the presence or in the absence of an added organic solvent.
  • a solvent it may be, for example, benzene, toluene, iso-propanol, diethyl ether, cyclohexanone, or a mixture of aldehyde condensation products such as is disclosed in British Patent Specification No. 1338237.
  • the compound of formula (IV) can serve as a solvent for the catalyst species and the reaction product(s).
  • the reaction medium may further include excess triorganophosphine ligand.
  • excess triorganophosphine ligand typically at least about 2 moles up to about 100 moles or more, e.g. up to about 1000 moles or more, of excess free triorganophosphine per gram atom of rhodium may be present in the reaction medium.
  • the upper limit to the amount of free triorganophosphine will be set by its solubility in the reaction medium under the chosen hydroformylation conditions.
  • concentration of free triorganophosphine may range up to about 30% by weight or more, e.g. up to about 50% by weight, of the reaction medium.
  • the temperature of the reaction medium may range from a threshold temperature below which the catalyst is effectively inert up to a maximum temperature at which either the catalyst is destroyed or deactivated.
  • the reaction temperature when using a rhodium complex catalyst, ranges from room temperature upwards, for example from about 30°C up to about 120°C or more, e.g. up to about 160°C. It will usually be preferred to operate at a temperature of at least about 60°C, e.g. about 70°C to about 110°C.
  • the partial pressure of hydrogen when using a rhodium complex catalyst, may range from about 0.1 kg/cm2 absolute up to about 10 kg/cm 2 absolute or more, e.g. up to about 20 kg/cm 2 absolute.
  • the partial pressure of carbon monoxide may range also from about 0.1 kg/cm2 absolute up to about 10 kg/cm 2 absolute or more.
  • the triorganophosphine ligand may be an aliphatic phosphine, such as tributyl phosphine, but is preferably an aromatic phosphine, such as triphenylphosphine.
  • Other triorganophosphines that can be mentioned include tri-(naphthyl-1 )-phosphine, tri-(naphthyl-2)-phosphine, tri-(o-, m- or p-tolyl)-phosphine, tri-(o-, m- or p-methoxyphenyl)-phosphine, and p-N,N-dimethylaminophenyl diphenylphosphine.
  • the preferred tri-organophosphine is triphenylphosphine.
  • the process of the invention may be carried out discontinuously or batchwise, as for example in a pressurised batch reactor. However, it will usually be preferred to operate the process continuously.
  • the process can be conducted using a liquid recycle process in which reactor solution is passed to a product recovery zone from which catalyst-containing solution is recycled to the hydroformylation reactor.
  • a product recovery zone may, for example, comprise a distillation column maintained at a lower pressure than the pressure in the hydroformylation reactor so that the compound or compounds of formula (I) is or are recovered as an overhead vaporous product.
  • the compound of formula (IV) used as starting material can be prepared in conventional manner by reaction of allyl alcohol with an olefin of formula wherein R 1 , R 2 , R 3 and R 4 have the meanings ascribed to them above, in the presence of an acidic catalyst.
  • an acidic catalyst for example, iso-butylene, 2-methylbut-1-ene, 2-methylbut-2-ene, 2,3-dimethylbut-2-ene, 3-methylpent-2-ene, 2-ethylbut-1-ene.
  • 1-methyl-cyclohexene, and 1-methylcyclopentene Hence illustrative compounds of formula (IV) include:
  • the reaction with the olefin is conveniently effected in the presence of an acidic catalyst.
  • the etherification is a reversible reaction and is favoured by the use of low temperatures, for example a temperature in the range of from about 0°C to about 80°C.
  • a temperature in the range of from about 0°C to about 80°C usually it will be preferred to effect etherification of allyl alcohol at about 60°C or less, preferably in the range of from about 15°C to about 60°C for example in the range of from about 35°C to about 60°C.
  • the olefin may be volatile it may be necessary to effect the etherification reaction under elevated pressure.
  • Typical acidic catalysts include ion exchange resins, preferably in anhydrous form, containing sulphonic acid and/or carboxylic acid groups, such as Amberlyst 15 and Dowex 50 resins, as well as aqueous acids, e.g. aqueous solutions of phosphoric acid or dilute aqueous solutions of sulphuric acid (containing, for example, 10% w/v sulphuric acid or less), acid zeolites, acid clays, and organic acids such as p-toluenesulphonic acid or formic acid.
  • ion exchange resins preferably in anhydrous form, containing sulphonic acid and/or carboxylic acid groups, such as Amberlyst 15 and Dowex 50 resins, as well as aqueous acids, e.g. aqueous solutions of phosphoric acid or dilute aqueous solutions of sulphuric acid (containing, for example, 10% w/v sulphuric acid or less), acid zeolites,
  • compounds of formula (I) are useful intermediates for the production of other chemicals.
  • compounds of the formula (V) can be oxidised and then deetherified to form butyrolactone, as described in copending patent application No. 803011303 (Publication No. 0018162) filed simultaneously herewith, or can be reduced and then deetherified to form butane-1,4-dioi, as described in our copending patent application No. 80301131.1 (Publication No. 0018163) filed simultaneously herewith, or can be reduced, deetherified and cyclo-dehydrated to form tetrahydrofuran, as described in our copending patent application No. 80301132.9 (Publication No. 0018164) filed simultaneously herewith.
  • Filmer 351 is a complex mixture of polymeric condensation products of n- and iso-butyraldehydes of the type disclosed in British Patent Specification No. 1338237.
  • the autoclave was then sealed.
  • the body of the autoclave was immersed in an oil bath capable of being heated and thermostatically controlled to ⁇ 1 °C between 40°C and 180°C by means of a heater/stirrer.
  • the pressure within the reactor could be monitored by means of a pressure transducer linked to a single pen recorder.
  • the stirrer was switched on and its speed adjusted to 500 r.p.m.
  • the reactor was purged with a hydrogen/carbon monoxide gas mixture, the composition of which depended on the planned H 2 :CO ratio.
  • the reactor was then pressurised to a level which was 0.35 kg/cm 2 below the desired operating pressure and isolated.
  • the stirrer speed was then adjusted to 2000 r.p.m. and the temperature increased to the desired value.
  • the pressure was then increased to the required level using the same H Z/ CO mixture and the reactor isolated once more. Subsequently 10 ml of allyl t-butyl ether were pumped into the reactor, whereupon reaction commenced.
  • the rate of reaction was monitored by timing the pressure drop between two defined levels ⁇ 0.07 kg/cm 2 around the design pressure. When the pressure reached the lower defined level, the reactor was repressurised to a level 0.14 kg/cm 2 above the design operating pressure with an approximately 1:1 H 2 :CO mixture as demanded by the stoichiometric requirements of the reaction and the procedure repeated until the reaction was complete, at which time the rate of pressure drop was negligible.
  • the oil heater/stirrer was then switched off, the hot oil run out of the bath and replaced with cold oil.
  • the oil stirrer was switched on again and the reactor cooled to 40°C. The reactor stirrer was then switched off and the reactor depressurised and opened to permit the reaction solution to be removed for analysis and/or storage.
  • the autoclave was then purged with a 1:1 molar H 2 :CO mixture and pressurised to 2.1 kg/cm 2 absolute by closure of the outlet valve. Reaction commenced and proceeded smoothly with a slight exotherm at the beginning of the reaction. As the reaction proceeded, the pressure dropped; when the total pressure reached 1.9 kg/cm 2 absolute, more 1:1 H 2 :CO mixture was admitted to the autoclave to restore the pressure to 2.1 kg/cm 2 absolute. This repressurisation technique was repeated as necessary until no more gas was taken up, indicating that reaction was complete. This took between 3 and 4 hours. The autoclave was cooled, depressurised and opened, and the contents discharged and stored under nitrogen.
  • the ratios of the peak areas corresponded to the expected ratios as predicted from the respective assigned structural formula.
  • the quoted chemical shift is the centred value.
  • Example 2 The hydroformylation procedure of Example 2 was repeated utilising 90 ml of allyl 2,3-dimethylbut-2-yl ether in place of allyl t-butyl ether.
  • the selectivities achieved were as follows:-

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (10)

1. Aldéhydo-éthers de la formule générale suivante:
Figure imgb0025
dans laquelle R, et R2 représentent chacun, indépendamment l'un de l'autre, un radical alkyle de 1 à 4 atomes de carbone et R3 et R4 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un radical alkyle de 1 à 4 atomes de carbone ou bien où R1 représente un radical alkyle ayant de 1 à 4 atomes de carbone, R2 et R3 formant, conjointement avec les atomes de carbone auxquels ils sont liés un anneau cycloaliphatique à 5 ou 6 chaînons et où R4 représente un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, tandis que Y représente ―CH2― CH2―CH2― ou bien CH2―CH(CH3)―.
2. Aldéhydo-éthers selon la revendication 1, caractérisés en ce que R, et R2 représentent chacun, indépendamment l'un de l'autre, un groupe méthyle ou éthyle R3 représentant un atome d'hydrogène ou un groupe méthyle et R4 un atome d'hydrogène.
3. Le 4-t-butoxybutyraldéhyde.
4. Le 3-t-butoxy-2-méthylpropionaldéhyde.
5. Procédé pour préparer un aldéhydo-éther de la formule générale dans laquelle:
Figure imgb0026
dans laquelle R1 et R2 représentent chacun indépendamment l'un de l'autre, un radical alkyle de 1 à 4 atomes de carbone et R3 et R4 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un radical alkyle de 1 à 4 atomes de carbone ou bien où R1 représente un radical alkyle ayant de 1 à 4 atomes de carbone, R2 et R3 formant, conjointement avec les atomes de carbone auxquels ils sont liés un anneau cycloaliphatique à 5 ou 6 chaînons et où R4 représente un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, tandis que Y représente ―CH2― CH2―CH2― ou bien CH2―CH―(CH3)―, qui consiste à mettre en contact un composé de la formule générale:
Figure imgb0027
dans laquelle R1, R2, R3 et R4 ont la signification définie ci-dessus, avec de l'hydrogène et du monoxyde de carbone dans des conditions d'hydroformylation et en présence d'une quantité catalytique d'un catalyseur d'hydroformylation.
6. Procédé selon la revendication 5 caractérisé en ce que le catalyseur d'hydroformylation est un complexe de rhodium comprenant du rhodium en combinaison avec du monoxyde de carbone et du triorganophosphine comme ligand.
7. Procédé selon la revendication 6, caractérisé en ce qu'on met en contact un composé de la formule (IV) avec de l'hydrogène et du monoxyde de carbone en présence d'un catalyseur complexe de rhodium à une température comprise entre environ 30°C et jusqu'à 160°C et sous une pression totale d'environ 20 kg/cm2.
8. Procédé selon la revendication 6 ou la revendication 7, caractérisé en ce qu'on met en contact un composé de la formule (IV) avec de l'hydrogène et du monoxyde de carbone en présence d'un catalyseur complexe de rhodium à une concentration d'environ 20 ppm et allant jusqu'à environ 500 ppm de rhodium calculé sous la forme de métal, la pression partielle d'hydrogène s'échelonnant entre environ 0,1 kg/cm2 abs et environ 10 kg/cm2 abs, la pression totale du monoxyde de 10 carbone étant comprise entre environ 0,1 kg/cm2 abs et 10 kg/cm2 abs, tandis que la pression totale est d'environ 20 kg/cm2 abs ou moins.
9. Procédé selon l'une quelconque des revendications 5 à 8 caractérisé en ce que R, et R2 représentent chacun un radical méthyle et R3 et R4 représentent chacun un atome d'hydrogène.
10. Procédé selon l'une quelconque des revendications 6 à 9 caractérisé en ce qu'on met le composé de la formule (IV) en contact avec de l'hydrogène et du monoxyde de carbone en présence du catalyseur complexe de rhodium et en présence d'au moins deux moles de triorganophosphine libre par atome-gramme de rhodium.
EP80301129A 1979-04-11 1980-04-09 Aldéhyde-éthers et procédé pour leur préparation Expired EP0018161B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80301129T ATE3537T1 (de) 1979-04-11 1980-04-09 Aldehyd-aether und verfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7912849 1979-04-11
GB7912849 1979-04-11

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EP0018161A1 EP0018161A1 (fr) 1980-10-29
EP0018161B1 true EP0018161B1 (fr) 1983-05-25

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EP (1) EP0018161B1 (fr)
JP (1) JPS55141427A (fr)
KR (1) KR840000276B1 (fr)
AR (1) AR225920A1 (fr)
AT (1) ATE3537T1 (fr)
AU (1) AU536556B2 (fr)
BR (1) BR8002277A (fr)
CA (1) CA1136650A (fr)
DE (1) DE3063424D1 (fr)
ES (1) ES8101531A1 (fr)
IN (1) IN153492B (fr)
MX (1) MX151832A (fr)
PL (1) PL223392A1 (fr)
ZA (1) ZA802151B (fr)

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US4510080A (en) * 1982-04-06 1985-04-09 International Flavors & Fragrances Inc. Organoleptic uses of hydrocarbyloxy alkanals
EP0096987B1 (fr) * 1982-06-11 1985-11-13 DAVY McKEE (LONDON) LIMITED Procédé d'hydroformylation
US4599468A (en) * 1983-09-19 1986-07-08 International Flavors & Fragrances Inc. Ether carboxaldehydes
US4533756A (en) * 1983-11-07 1985-08-06 Texaco Inc. Process for synthesis of acrylic acid precursors via hydroformylation of vinyl ether
DE3403427A1 (de) * 1984-02-01 1985-08-01 Degussa Ag, 6000 Frankfurt Verfahren zur herstellung von 1,4-butandial
JPH0723876Y2 (ja) * 1986-08-01 1995-05-31 オムロン株式会社 動作表示灯付電気機器
US4891447A (en) * 1988-12-16 1990-01-02 Basf K&F Corporation Sandalwood odorants
EP0697014B2 (fr) † 1993-05-06 2002-08-28 Dsm N.V. Procede de preparation d'un compose organique d'aldehyde lineaire

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US2170854A (en) * 1936-02-24 1939-08-29 Carbide & Carbon Chem Corp Methoxy acetaldehyde and process of making alkoxy acetaldehydes
US2555950A (en) * 1949-06-23 1951-06-05 Du Pont Preparation of 2-methoxy-1-alkanols and 2-methoxy-1-alkanals
DE891690C (de) * 1950-05-22 1953-10-01 Distillers Co Yeast Ltd Verfahren zur Herstellung von ª‰-Alkoxyaldehyden
US3239570A (en) * 1960-07-22 1966-03-08 Shell Oil Co Hydroformylation of olefins
US3676500A (en) * 1967-01-26 1972-07-11 Du Pont Tertiary aldehyde compounds
US3527809A (en) * 1967-08-03 1970-09-08 Union Carbide Corp Hydroformylation process
US3518310A (en) * 1968-02-09 1970-06-30 Shell Oil Co Preparation of beta-hydroxypropionaldehyde and beta-alkoxypropionaldehydes
GB1298331A (en) * 1968-08-02 1972-11-29 Johnson Matthey Co Ltd Improved hydroformylation process
GB1338237A (en) * 1969-12-22 1973-11-21 Union Carbide Corp Hydroformylation process
US3917661A (en) * 1970-01-07 1975-11-04 Union Carbide Corp Hydroformylation of unsaturated organic compounds
US3764712A (en) * 1970-11-24 1973-10-09 Fritzsche Dodge & Olcott Inc Compositions containing hexoxyacetaldehydes and their derivatives
CA1022934A (en) * 1972-11-29 1977-12-20 Donald E. Morris Hydroformylation process
US4064145A (en) * 1975-10-20 1977-12-20 Celanese Corporation Production of tetrahydrofuran
US4029710A (en) * 1976-03-31 1977-06-14 Chevron Research Company 4-Alkoxy-N-butyraldehyde preparation
JPS54119407A (en) * 1978-03-09 1979-09-17 Agency Of Ind Science & Technol Preparation of aldehydes
EP0018162A1 (fr) * 1979-04-11 1980-10-29 DAVY McKEE (LONDON) LIMITED Production de butyrolactone

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ATE3537T1 (de) 1983-06-15
AU5734780A (en) 1980-10-16
BR8002277A (pt) 1980-12-02
KR830002664A (ko) 1983-05-30
US4414420A (en) 1983-11-08
ZA802151B (en) 1981-05-27
IN153492B (fr) 1984-07-21
AR225920A1 (es) 1982-05-14
MX151832A (es) 1985-04-01
KR840000276B1 (ko) 1984-03-13
ES490987A0 (es) 1980-12-16
EP0018161A1 (fr) 1980-10-29
CA1136650A (fr) 1982-11-30
JPS55141427A (en) 1980-11-05
DE3063424D1 (en) 1983-07-07
PL223392A1 (fr) 1981-01-30
AU536556B2 (en) 1984-05-10
US4383125A (en) 1983-05-10
JPS6332773B2 (fr) 1988-07-01
ES8101531A1 (es) 1980-12-16

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